Compositions comprising set retarder compositions and associated methods

ABSTRACT

Cement compositions comprising set retarder compositions, and methods of using the cement compositions in surface and subterranean applications are provided. In some embodiments, cement compositions are provided that comprise a hydraulic cement comprising an API cement, water, and a set retarder composition, the set retarder composition comprising an acrylamide polymer derivative; and an iron compound. In other embodiments, cement compositions, set retarder compositions, methods of cementing, methods of retarding the set time of a cement composition, and methods of preparing a cement composition are provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No. 10/608,748 entitled “Cement Compositions with Improved Fluid Loss Characteristics and Methods of Cementing in Surface and Subterranean Applications,” filed on Jun. 27, 2003.

BACKGROUND

The present invention relates to cementing operations, and more particularly, to cement compositions comprising set retarder compositions and methods of using the cement compositions in surface and subterranean applications.

Hydraulic cement compositions are commonly utilized in subterranean operations, particularly subterranean well completion and remedial operations. For example, hydraulic cement compositions are used in primary cementing operations whereby pipe strings such as casings and liners are cemented in well bores. In performing primary cementing, hydraulic cement compositions are pumped into the annular space between the walls of a well bore and the exterior surface of a pipe string disposed therein. The cement composition is permitted to set in the annular space, thereby forming an annular sheath of hardened substantially impermeable cement therein that substantially supports and positions the pipe string in the well bore and bonds the exterior surface of the pipe string to the walls of the well bore. Hydraulic cement compositions also are used in remedial cementing operations such as plugging highly permeable zones or fractures in well bores, plugging cracks and holes in pipe strings, and the like.

Set retarder compositions are a common additive that may be included in cement compositions, inter alia, to delay the set time of the cement composition. Among other things, set retarder compositions may be useful not only in delaying the set time of a cement composition exposed to high subterranean temperatures, but also to extend the time the cement composition may remain pumpable after the cement composition is mixed before it is placed into the desired location. While a variety of set retarder compositions have been developed and used successfully, they have drawbacks. For instance, conventional set retarder compositions may include lignosulfonates that may provide unpredictable retardation of the cement compositions set time. Furthermore, synthetic polymers also have been used as set retarder compositions with some success. These synthetic polymers, however, may be difficult to produce, which may add undesirable expense to the cementing operation.

Set retarder compositions also have been added to cement compositions for gel strength modification. When a cement composition becomes static, it develops a property commonly referred to as “gel strength.” Gel strength is not compressive strength. Generally, there are two phases in the development of gel strength: “zero-gel time” and “transition time.” Zero-gel time, which may also be referred to as “delayed-gel time”, refers to the time period required for a cement composition to reach a gel strength of about 100 lbs per 100 ft². During the zero-gel time, it is believed that the cement composition retains the ability to transmit hydrostatic pressure. Accordingly, the cement composition may be able to prevent the influx of formation fluids (e.g., gas) into the cement composition from the subterranean formation and associated problems. The “transition time” of a cement composition refers to the period when the cement composition has sufficient gel strength to support itself yet cannot prevent the influx of formation fluids (e.g., gases), and ending when the cement composition achieves sufficient gel strength to prevent the influx of such formation fluids. Experimentally, the transition time may be approximated by measuring the time period in which the gel strength of a cement composition progresses from about 100 lbs per 100 ft² to about 500 lbs per 100 ft². Additives may be added to a cement composition for gel strength modification, inter alia, to increase the zero-gel time of a cement composition and/or accelerate the transition time of a cement composition. Additives for gel strength modification include synthetic polymers, such as copolymers of 2-acrylamido-2-methylpropanesulfonic acid and N,N-dimethylacrylamide; and polymers having a tannin backbone, wherein the tannin backbone has grafted thereto a graft portion consisting of vinylamide derivatives. While these additives have been developed and used successfully, the complexity associated with their production may add undesirable expense to the cementing operation.

SUMMARY

The present invention relates to cementing operations, and more particularly, to cement compositions comprising set retarder compositions and methods of using the cement compositions in surface and subterranean applications.

In one embodiment, the present invention provides a cement composition that comprises a cement comprising an API cement, water, and a set retarder composition, the set retarder composition comprising an acrylamide polymer derivative and an iron compound.

In another embodiment, the present invention provides a cement composition that comprising a cement, water, and a set retarder composition, the set retarder composition comprising a lignin-based retarder and an iron compound.

In another embodiment, the present invention provides a set retarder composition that comprises an acrylamide polymer derivative and an iron compound.

In another embodiment, the present invention provides a method of cementing in a subterranean formation that comprises providing a cement composition comprising a cement comprising an API cement, water, and a set retarder composition, the set retarder composition comprising an acrylamide polymer derivative and an iron compound; placing the cement composition into the subterranean formation; and permitting the cement composition to set therein.

In another embodiment, the present invention provides a method of cementing in a subterranean formation that comprises providing a cement composition comprising a cement, water, and a set retarder composition, the set retarder composition comprising a lignin-based retarder and an iron compound; placing the cement composition into the subterranean formation; and permitting the cement composition to set therein.

In another embodiment, the present invention provides a method of retarding the set time of a cement composition that comprises adding a set retarder composition to a cement composition, the set retarder composition comprising an acrylamide polymer derivative, and an iron compound; placing the cement composition into the subterranean formation; and permitting the cement composition to set therein.

In another embodiment, the present invention provides a method of preparing a cement composition that comprises preblending a set retarder composition that comprises an acrylamide polymer derivative and an iron compound; and preparing a cement composition that comprises the set retarder composition, a cement, and water, subsequent to preblending the set retarder composition.

The objects, features and advantages of the present invention will be readily apparent to those skilled in the art upon a reading of the detailed description that follows.

DETAILED DESCRIPTION

The present invention relates to cementing operations, and more particularly, to cement compositions comprising set retarder compositions and methods of using the cement compositions in surface and subterranean applications. While the compositions and methods of the present invention are useful in a variety of applications, they may be particularly useful for subterranean well completion and remedial operations, such as primary cementing, e.g., cementing casings and liners in well bores, including those in production wells, which include multi-lateral subterranean wells. They are also useful for surface cementing operations, including construction cementing operations.

The cement compositions of the present invention generally comprise a cement, water, and a set retarder composition of the present invention. A wide variety of optional additives may be included in the cement compositions of the present invention if desired. The cement compositions of the present invention may range in density from about 5 lb/gallon to about 30 lb/gallon. In one embodiment, the cement compositions of the present invention range in density from about 8 lb/gallon to about 20 lb/gallon.

Any cements suitable for use in subterranean applications are suitable for use in the present invention. Furthermore, cements suitable for use in surface applications, e.g., construction cements, may be suitable for use in the present invention. In one embodiment, the improved cement compositions of the present invention comprise a hydraulic cement. A variety of hydraulic cements are suitable for use including those comprised of calcium, aluminum, silicon, oxygen, and/or sulfur, which set and harden by reaction with water. Such hydraulic cements include, but are not limited to, Portland cements, pozzolanic cements, gypsum cements, high alumina content cements, silica cements, high alkalinity cements, and mixtures thereof. In some embodiments, the hydraulic cement comprises an API cement. The API cement may comprise API Classes A, B, C, G, H, or J Portland cements, or equivalents thereof. The above-mentioned API cements are defined and described in API Specification for Materials and Testing for Well Cements, API Specification 10A, 22nd Edition, dated Jan. 1, 1995 of the American Petroleum Institute.

The water utilized in the cement compositions of the present invention may be fresh water, saltwater (e.g., water containing one or more salts dissolved therein), brine (e.g., saturated saltwater), or seawater. Generally, the water may be from any source provided that it does not contain an excess of compounds that adversely affect the cement compositions. The water may be present in an amount sufficient to form a pumpable slurry. Generally, the water is present in the cement compositions of the present invention in an amount in the range of from about 15% to about 200% by weight of cement (“bwoc”) therein. In certain embodiments, the water is present in the cement compositions of the present invention in an amount in the range of from about 25% to about 60% bwoc therein.

The set retarder compositions of the present invention generally comprise an iron compound and at least one of an acrylamide polymer derivative or a lignin-based retarder. Optionally, set retarder compositions of the present invention may further comprise hydratable polymers, dispersants, zeolites, shales, organic acids, silicas, deaggregation agents, or combinations thereof. Furthermore, in some embodiments the set retarder compositions of the present invention further may function as dispersants, inter alia, to reduce the apparent viscosity of the slurry to permit the pumping of the cement slurry with less friction pressure, and less hydraulic horsepower. In some embodiments, the set retarder compositions of the present invention further may function as free flow additives, wherein the set retarder compositions of the present invention may be blended with the cement, prior to its combination with water, to improve the ability of the dry cement to flow freely. Furthermore, in some embodiments, the set retarder compositions of the present invention further may function to provide gel strength modification, for example, by accelerating the transition time of the cement composition.

In some embodiments, the set retarder compositions of the present invention comprise an acrylamide polymer derivative. Any polymer or salt thereof capable of retarding or delaying the set time of a cement composition and comprising monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or derivatives thereof (e.g., acid salts of 2-acrylamido-2-methylpropane sulfonic acid) will be an “acrylamide polymer derivative” as that term is used herein. In some embodiments, the acrylamide polymer derivative may be a copolymer or a terpolymer. Generally, monomers formed from 2-acrylamido-2methylpropane sulfonic acid or derivatives thereof have the following structure:

wherein M is hydrogen, ammonium, sodium, or potassium.

An example of a suitable acrylamide polymer derivative comprises a copolymer comprising first monomers formed from a hydrolyzed acrylamide, partially hydrolyzed acrylamide, a hydrolyzed acrylamide derivative, or a partially hydrolyzed acrylamide derivative and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or derivatives thereof. Another example of a suitable acrylamide polymer derivative comprises a copolymer comprising first monomers formed from acrylic acid and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or derivatives thereof. An example of a suitable copolymer comprising first monomers formed from acrylic acid and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or derivatives thereof is commercially available under the trade designation “SCR-100™” retarder from Halliburton Energy Services, Inc., Duncan, Okla. In certain embodiments, where the acrylamide polymer derivative comprises a copolymer comprising first monomers formed from acrylic acid and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or derivatives thereof, the second monomers may be present in the copolymer in an amount in the range of from about 40 mole percent (“%”) to about 60 mole % with the remainder of the copolymer comprising the first monomers, in other embodiments, the second monomers may be present in an amount in the range of from about 45 mole % to about 55 mole %, and, in other embodiments, the second monomer may be present in an amount of about 50 mole %.

Another example of a suitable acrylamide polymer derivative is a copolymer comprising first monomers formed from a first acid and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or derivatives thereof, wherein the first acid is represented by the formula:

wherein: R₁ is H or CH₃, R₂ is H or COOH, R₃ is H or COOH, and R₄ is H, COOH, or CH₂COOH; provided that when R₁ is H and R₂ is COOH, R₃ and R₄ are different and are either H or COOH; when R₁ and R₂ are both H, R₃ is COOH and R₄ is CH₂COOH; and when R₁ is CH₃, R₂ is COOH and R₃ and R₄ are different and are either H or COOH. Examples of suitable acids within the scope of the above structure are maleic acid, itaconic acid, fumaric acid, citraconic acid, mesaconic acid, and other similar acids. An example of a suitable acrylamide polymer derivative that comprises a copolymer comprising first monomers formed from maleic acid and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or derivatives thereof is commercially available under the trade designation “SCR-500™” retarder from Halliburton Energy Services, Inc., Duncan, Okla. In certain embodiments, where the acrylamide polymer derivative comprises a copolymer comprising monomers formed from a first acid, as described above, and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or derivatives thereof, the first monomers may be present in the copolymer in an amount in the range of from about 5 mole % to about 50 mole % with the remainder of the copolymer comprising the second monomer, and, in other embodiments, the first monomers may be present in an amount in the range of from about 30 mole % to about 50 mole %.

Another example of a suitable acrylamide polymer derivative comprises a terpolymer comprising a first monomer formed from a first acid, as described above, second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or derivatives thereof, and third monomers different from the first monomers and the second monomers. In some embodiments, the third monomers are formed from maleic acid, acrylic acid, sodium methallyl sulfonate, sodium-p-sulfophenyl methallyl ether, sodium p-vinyl benzene sulfonate, acrylamide, N,N-dimethylacrylamide, vinyl sulfonic acid, acrylonitrile, 1-vinyl-2-pyrrolidone, vinyl phosphonic acid, diallydimethylammonium chloride, water soluble acrylates, methacrylates, acrylamide derivatives, or cationic monomers, such as dimethylaminoethyl methacrylatemethylchloride, diethylaminoethyl methacrylate, dimethyl aminoethyl acrylate methyl chloride, N-dimethyl aminopropyl methacrylamide, methacrylamido propyltrimethyl ammonium chloride, N,N-dimethylaminoethyl methacrylate, and 2-triethylammoniummethyl methacrylate chloride, or the like. Generally, in some embodiments, the first monomers may be present in the terpolymer in an amount in the range of from about 5 mole % to about 50 mole %, the second monomers may be present in the terpolymer in an amount in the range of from about 90 mole % to about 45 mole %, and the third monomers may be present in the terpolymer in an amount in the range of from about 5 mole % to about 50 mole %.

Generally, the acrylamide polymer derivatives included in the set retarder compositions of the present invention may be manufactured in accordance with any suitable technique for polymer manufacture, such as any of a variety of free radical techniques. Examples of suitable acrylamide polymer derivatives are described in U.S. Pat. Nos. 4,941,536 and 5,536,311, the relevant disclosure of which are incorporated herein by reference. In certain embodiments, the acrylamide polymer derivative may have a weight average molecular weight of below about 50,000.

As those of ordinary skill in the art will appreciate, certain acrylamide polymer derivatives may have little impact on the set retardation of a cement composition. For example, certain acrylamide polymer derivatives may have little impact on the set retardation of a cement composition in wells having a bottom hole static temperature (“BHST”) of greater than about 200° F. For example, acrylamide polymer derivatives that comprise a copolymer comprising monomers formed from N,N-dimethylacrylamide and monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or acid salts thereof may have little impact on set retardation in wells having a BHST of greater than about 200° F. One of ordinary skill in the art, with the benefit of this disclosure, will be able to determine other acrylamide polymer derivatives that may have little impact on the set retardation of a cement composition.

Generally, the acrylamide polymer derivative may be present in the set retarder composition of the present invention in an amount in the range of from about 1% to about 95% by weight. In some embodiments, the acrylamide polymer derivative is present in the set retarder composition of the present invention in an amount in the range of from about 30% to about 60% by weight. In some embodiments, the acrylamide polymer derivative is present in the set retarder composition of the present invention in an amount of about 45% to about 50% by weight.

In other embodiments, the set retarder compositions of the present invention may comprise a lignin-based retarder. As referred to herein, a “lignin-based retarder” refers to any suitable composition comprising a lignosulfonate, wherein the composition is capable of delaying the set time of a cement composition. Lignosulfates generally comprise metallic sulfonate salts made from the lignin of sulfite pulp mill liquor. In some embodiments, the lignin-based retarder comprises a lignosulfonate and a sulfonated lignin. The sulfonated lignin may be produced by the kraft process, e.g., a sulfonate kraft lignin. The sulfonated lignin should contain at least about 2% ogranic sulphur, and, in some embodiments, contain in the range of from about 3.5% to about 7% organic sulphur. In another embodiment, the lignin-based retarder further comprises a sugar acid. In an exemplary embodiment, the sugar acid included in the lignin-based retarder is derived from xylose, e.g., xylose sugar acid. In some embodiments, the lignin-based retarder comprises about 59 parts by weight lignosulfonate, about 11 parts by weight sugar acid, and about 30 parts by weight sulfonated lignin. An example of a suitable lignin-based retarder is commercially available under the trade name “HR-601” from Halliburton Energy Services, Duncan, Okla. Examples of suitable lignin-based retarders are described in U.S. Pat. No. 6,227,294 and U.S. Pat. No. 6,372,037, the relevant disclosures of which are incorporated herein by reference.

Generally, the lignin-based retarder may be present in the set retarder composition of the present invention in an amount in the range of from about 1% to about 95% by weight. In some embodiments, the lignin-based retarder is present in the set retarder composition of the present invention in an amount in the range of from about 30% to about 60% by weight. In some embodiments, the lignin-based retarder is present in the set retarder composition of the present invention in an amount of about 45% to about 50% by weight.

The set retarder compositions of the present invention further comprise iron compounds. Suitable iron compounds include any soluble iron compound that functions with the acrylamide polymer derivatives to provide set retardation of a cement composition, including, but not limited to, iron chloride and iron gluconates. Generally, the iron chloride may be ferrous chloride, ferric chloride, or mixtures thereof. The iron compound functions, inter alia, in combination with other components which may be present, to aid the cement composition in hydrating in a predictable manner. Inter alia, the iron compound component may also improve the compressive strength of the cement composition in which it is used. Furthermore, it is believed that the iron compound may have synergistic effects with the acrylamide polymer derivative that may reduce the amount of an acrylamide polymer derivative needed to provide a desired level of set retardation. In one embodiment, the iron chloride used in the set retarder compositions of the present invention is anhydrous ferric chloride. An example of a suitable source of anhydrous ferric chloride is commercially available from BASF Corporation in Germany. Another source of a suitable iron chloride is a multi-purpose cement additive commercially available under the trade designation “UNIVERSAL CEMENT SYSTEMS™” from Halliburton Energy Services, Inc., of Duncan, Okla.; such additive is disclosed in U.S. Pat. Nos. 5,749,418; 5,968,255; and 5,972,103, the relevant disclosures of which are herein incorporated by reference. Generally, in some embodiments, Universal Cement Systems™ multi-purpose cement additive may comprise in the range from about 0.5% to about 30% iron chloride by weight. The iron compound is generally present in the set retarder composition of the present invention in an amount sufficient to allow the cement to be suitable for the subterranean environment of the well being cemented. In some embodiments, the iron compound is present in the set retarder composition of the present invention in an amount in the range of from about 5% to about 25% by weight. In some embodiments, the iron compound is present in the set retarder composition of the present invention in an amount in the range of from about 10% to about 15% by weight.

Optionally, the set retarder compositions of the present invention may comprise a dispersant. Where present, the dispersant acts, inter alia, to control the rheology of the cement composition and to stabilize the cement composition over a broad density range. While a variety of dispersants known to those skilled in the art may be used in accordance with the present invention, a suitable dispersant is a water-soluble polymer prepared by the caustic-catalyzed condensation of formaldehyde with acetone wherein the polymer contains sodium sulfate groups. Such a dispersant is commercially available under the trade designation “CFR-3™” from Halliburton Energy Services, Inc., Duncan, Okla. Another suitable dispersant is commercially available under the trade designation “CFR-2™,” also from Halliburton Energy Services, Inc., of Duncan, Okla. Another source of a suitable dispersant is a multi-purpose cement additive commercially available under the trade designation “UNIVERSAL CEMENT SYSTEMS™” from Halliburton Energy Services, Inc., of Duncan, Okla.; such additive is disclosed in U.S. Pat. Nos. 5,749,418; 5,968,255; and 5,972,103, the relevant disclosures of which are incorporated herein by reference. Generally, in some embodiments, Universal Cement Systems™ multi-purpose cement additive may comprise in the range of from about 5% to about 70% of a dispersant by weight. Where used, the dispersant is present in the set retarder composition of the present invention in an amount sufficient to prevent gelation of the cement composition. In some embodiments, the dispersant is present in the set retarder composition of the present invention in an amount in the range of from about 5% to about 70% by weight. In some embodiments, the dispersant is present in the set retarder composition of the present invention in an amount in the range of from about 20% to about 40% by weight.

Optionally, the set retarder compositions of the present invention may comprise a hydratable polymer. Where present, the hydratable polymer acts, inter alia, to increase the viscosity of the cement composition in which the set retarder composition of the present invention is used. Various hydratable polymers can be utilized in the set retarder compositions including, but not limited to, carboxymethylcellulose, hydroxyethylcellulose, carboxymethylhydroxyethylcellulose, vinyl sulfonated polymers, and hydratable graft polymers. An example of a suitable hydratable polymer is a cellulose derivative commercially available from Dow Chemical Co., under the trade name “CARBOTRON 20.” Another source of a suitable hydratable polymer is a multi-purpose cement additive commercially available under the trade designation “UNIVERSAL CEMENT SYSTEMS™” from Halliburton Energy Services, Inc., of Duncan, Okla.; such additive is disclosed in U.S. Pat. Nos. 5,749,418; 5,968,255; and 5,972,103, the relevant disclosures of which are herein incorporated by reference. Generally, in some embodiments, the Universal Cement Systems™ multi-purpose cement additive may comprise in the range from about 1% to about 20% of a hydratable polymer by weight. Where used, the hydratable polymer is present in the set retarder composition of the present invention in an amount sufficient to contribute a desired degree of viscosity to the cement composition. In some embodiments, the hydratable polymer is present in the set retarder composition of the present invention in an amount in the range of from about 0.1% to about 15% by weight. In some embodiments, the hydratable polymer is present in the set retarder composition in an amount in the range of from about 1.0% to about 5% by weight.

Optionally, the set retarder compositions of the present invention may comprise a zeolite. Where used, the zeolite functions, inter alia, to improve the suspension of the set retarder compositions of the present invention in a cement composition. The zeolite comprises a mixture of chabazite and amorphous silica. The chabazite is present in the zeolite in an amount in the range of from about 50% to about 75% by weight. In some embodiments, the chabazite is present in the zeolite in an amount in the range of from about 65% to about 70% by weight. The amorphous silica is generally present in the zeolite in an amount in the range of from about 25% to about 50% by weight. In some embodiments, the amorphous silica is present in the zeolite in an amount in the range of from about 30% to about 35% by weight. An example of a suitable source of zeolite is available from the C2C Zeolite Corporation of Calgary, Canada. Where used, the zeolite is generally present in the set retarder composition of the present invention in an amount in the range of from about 0.1% to about 15% by weight. In certain embodiments, the zeolite is present in the set retarder composition of the present invention in an amount in the range of from about 3% to about 7% by weight.

The set retarder compositions of the present invention also may optionally comprise shale. Where used, the shale functions, inter alia, to improve the ability of the set retarder composition to flow freely as a powder. A variety of shales are suitable, including those comprised of silicon, aluminum, calcium, and/or magnesium. In some embodiments, the shale is vitrified shale. In certain embodiments, the vitrified shale may be fine grain vitrified shale, wherein the fine grain vitrified shale has a particle size distribution in the range of from about 2 to about 4,750 micrometers. An example of a suitable fine grain vitrified shale is “PRESSURE-SEAL® FINE LCM,” which is commercially available from TXI Energy Services, Inc., Houston, Tex. In another embodiment, the vitrified shale may be coarse grain vitrified shale, wherein the coarse vitrified shale particles may have a particle size distribution in the range of from about 2 micrometers to about 4,750 micrometers. An example of a suitable coarse grain vitrified shale is “PRESSUR-SEAL® COARSE LCM,” which is commercially available from TXI Energy Services, Inc., Houston, Tex. Where used, the shale is generally present in the set retarder composition of the present invention in an amount in the range of from about 0.1% to about 15% by weight. In certain embodiments, the shale is present in the set retarder composition of the present invention in an amount in the range of from about 3% to about 7% by weight.

Optionally, the set retarder compositions of the present invention further may comprise an organic acid. Where present, the organic acid acts, inter alia, to maintain the viscosity of the cement composition in which the set retarder composition of the present invention is included over a broad density range by helping to prevent gelation of the cement composition. Various organic acids can be included in the set retarder composition including, but not limited to, tartaric acid, citric acid, gluconic acid, oleic acid, phosphoric acid, and uric acid. An example of a suitable organic acid is commercially available from Halliburton Energy Services, Inc., of Duncan, Okla., under the trade name “HR®-25.” A suitable organic acid also may be included in Universal Cement Systems™ multi-purpose cement additive in an amount in the range of from about 0.01% to about 10% by weight. Other examples of suitable organic acids include, for example, organic acids which have either minimal or no effect on retarding or accelerating the setting of the cement. One of ordinary skill in the art with the benefit of this disclosure will recognize the types of organic acids which are appropriate for inclusion in the set retarder compositions of the present invention. Where used, the organic acid is present in the set retarder compositions in an amount sufficient to provide a desired degree of viscosity control. In some embodiments, the organic acid is present in the set retarder composition of the present invention in an amount in the range of from about 0.01% to about 5% by weight. In some embodiments, the organic acid is present in the set retarder composition of the present invention in an amount in the range of from about 0.01% to about 2% by weight.

Optionally, the set retarder compositions of the present invention may contain a deaggregation agent. Where used, the deaggregation agent functions, inter alia, to improve the ability of the set retarder composition of the present invention to flow freely as a powder. The deaggregation agent may also contribute a minor source of silica to the set retarder composition. An example of a suitable deaggregation agent is commercially available from National Pigment and Chemical Co. under the trade name Mica/Brite X150. Alternatively, quartz or ground sand may be used, though the spherical nature of Mica/Brite X150 particles is thought to contribute to improved flow characteristics for the cement composition. A suitable deaggregation agent also may be included in Universal Cement Systems™ multi-purpose cement additive in an amount in the range of from about 1% to about 30% by weight. Where used, the deaggregation agent is present in the set retarder composition of the present invention in an amount sufficient to enable the set retarder composition of the present invention to flow freely as a powder. In some embodiments, the deaggregation agent is present in the set retarder composition of the present invention in an amount in the range of from about 1% to about 15% by weight. In some embodiments, the deaggregation agent is present in the set retarder composition of the present invention in an amount in the range of from about 1% to about 10% by weight.

Optionally, the set retarder compositions of the present invention may comprise a source of silica. Where present, the silica assists in maintaining the compressive strength of the cement composition after setting. An example of a suitable source of high surface area amorphous silica is commercially available from Halliburton Energy Services, Inc., of Duncan, Okla., under the trade name “SILICALITE.” A suitable source of silica also may be included in Universal Cement Systems™ multi-purpose cement additive in an amount in the range of from about 1% to about 50% by weight. Where used, the high surface area amorphous silica is present in a set retarder composition of the present invention in an amount sufficient to provide a desired after-set compressive strength. In some embodiments, the high surface area amorphous silica is present in the set retarder composition of the present invention in an amount in the range of from about 0.1% to about 15% by weight. In one embodiment, the high surface area amorphous silica is present in the set retarder composition of the present invention in an amount in the range of from about 1% to about 5% by weight.

Generally, the set retarder compositions of the present invention should be present in the cement compositions of the present invention in an amount sufficient to provide the desired set retardation in the cement compositions of the present invention. The amount of a particular set retarder composition to include generally depends on a number of factors, including the bottom hole circulating temperature of the well, the particular set retarder composition chosen, and other factors known to those of ordinary skill in the art. In some embodiments, the quantity of the set retarder composition to be included in the cement composition may be determined prior to preparation of the cement composition. For example, the quantity of the set retarder composition to be included in the cement composition may be determined by performing thickening time tests of the type described in API Specification 10A, Twenty-Third Edition, April, 2002. More particularly, in certain embodiments, the set retarder composition of the present invention is present in the cement composition in an amount in the range of from about 0.01% to about 10% bwoc. In some embodiments, the set retarder composition of the present invention is present in the cement composition in an amount in the range of from about 0.01% to about 5% bwoc.

The set retarder compositions of the present invention may be prepared in a variety of forms, including, inter alia, particulates, solutions, suspensions. In some embodiments, it is believed that preblending of the components of a set retarder composition prior to their combination with the other components of the cement composition may aid the functionality of the set retarder composition. For example, the set retarder composition of the present invention may be formed by preblending an acrylamide polymer derivative with an iron compound. Furthermore, additional components, such as dispersants, hydratable polymers, zeolite, shale, organic acids, deaggregation agents, silicas, and combinations thereof, may be preblended with the acrylamide polymer derivative and the iron compound to form the set retarder composition. In some embodiments, preblending may include dry blending the acrylamide polymer derivative, the iron compound, and any other optional components of the set retarder composition, for example, where the set retarder composition is provided in particulate form. In other embodiments, preblending the set retarder composition may include preparing a solution or a suspension that comprises the acrylamide polymer derivative, the iron compound, and any other optional components of the set retarder composition. Furthermore, the cement compositions of the present invention may be prepared using any suitable methodology. In some embodiments, the components of the set retarder composition of the present invention may be preblended prior to the preparation of the cement composition. Next, the cement composition is prepared by combining the cement, water, and set retarder composition. In some embodiments, for example, where the set retarder composition is provided as a solution or a suspension, the set retarder composition may first be added to the water prior to their combination with the cement. In other embodiments, for example, when desired to improve the flow characteristics of the dry cement, the preblended set retarder composition, in particulate form, may be combined (e.g., dry blended) with the cement prior to their combination with the water. In other embodiments, the components of the set retarder composition may be individually added to the cement, water, and/or a combination thereof as desired by one skilled in the art.

As will be recognized by those skilled in the art, the cement compositions of this invention also may include additional suitable additives, including, inter alia, accelerants, defoamers, microspheres, fiber, weighting materials, salts, vitrified shale, fly ash, and the like. Any suitable additive may be incorporated within the cement compositions of the present invention. One of ordinary skill in the art with the benefit of this disclosure will be able to recognize where a particular additive is suitable for a particular application.

In one embodiment, the present invention provides a cement composition that comprises a cement comprising an API cement, water, and a set retarder composition, the set retarder composition comprising an acrylamide polymer derivative and an iron compound.

In another embodiment, the present invention provides a cement composition that comprising a cement, water, and a set retarder composition, the set retarder composition comprising a lignin-based retarder and an iron compound.

In another embodiment, the present invention provides a set retarder composition that comprises an acrylamide polymer derivative and an iron compound. An example of a set retarder composition of the present invention comprises 50% of an acrylamide polymer derivative (SCR-100™) by weight and 50% of Universal Cement Systems™ multi-purpose cement additive by weight. Another example of a set retarder composition of the present invention comprises 47.5% of an acrylamide polymer derivative (SCR-100™) by weight, 47.5% of Universal Cement Systems™ multi-purpose cement additive by weight, and 5.0% of zeolite by weight. Another example of a set retarder composition of the present invention comprises 47.5% of an acrylamide polymer derivative (SCR-100™) by weight, 47.5% of Universal Cement Systems™ multi-purpose cement additive by weight, and 5.0% of vitrified shale by weight.

In another embodiment, the present invention provides a method of cementing in a subterranean formation that comprises providing a cement composition comprising a cement comprising an API cement, water, and a set retarder composition, the set retarder composition comprising an acrylamide polymer derivative and an iron compound; placing the cement composition into the subterranean formation; and permitting the cement composition to set therein.

In another embodiment, the present invention provides a method of cementing in a subterranean formation that comprises providing a cement composition comprising a cement, water, and a set retarder composition, the set retarder composition comprising a lignin-based retarder and an iron compound; placing the cement composition into the subterranean formation; and permitting the cement composition to set therein.

In another embodiment, the present invention provides a method of retarding the set time of a cement composition that comprises adding a set retarder composition to a cement composition, the set retarder composition comprising an acrylamide polymer derivative, and an iron compound; placing the cement composition into the subterranean formation; and permitting the cement composition to set therein.

In another embodiment, the present invention provides a method of preparing a cement composition that comprises preblending a set retarder composition that comprises an acrylamide polymer derivative and an iron compound; and preparing a cement composition that comprises the set retarder composition, a cement, and water, subsequent to preblending the set retarder composition.

To facilitate a better understanding of the present invention, the following illustrative examples of some of the preferred exemplary embodiments are given. In no way should such examples be read to limit, or define, the scope of the invention.

EXAMPLE 1

Sample compositions were prepared according to the following procedure. Each sample was dry blended, then mixed for 35 seconds at 15,000 rpm in a Waring blender. After sample preparation, compressive strength tests and thickening time tests were performed on each of the samples using an ultrasonic cement analyzer according to API Specification 10A, Twenty-Third Edition, April, 2002. Furthermore, the time for each of the samples to reach a compressive strength of 50 psi and 500 psi, respectively, was recorded. Each sample composition was brought up to 220° F. and 3,000 psi in 60 minutes. Next, the sample compositions were brought up to 250° F. in 240 minutes while static. Thickening time tests were performed at 220° F.

Sample Composition No. 1 (comparative) was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, 0.5% of an acrylamide polymer derivative (SCR-100™) bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The crystalline or non-crystalline silica used in these examples has a particle size in the range of from about 2 to about 2,000 microns. HALAD® 344 is a fluid loss control additive that is commercially available from Halliburton Energy Services, Duncan, Okla. The thickening time was found to be 4 hours and 33 minutes at 220° F.

Sample Composition No. 2 was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, 1% of a set retarder composition of the present invention bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The set retarder composition of the present invention comprised an acrylamide polymer derivative (SCR-100™) and Universal Cement Systems™ multi-purpose cement additive in a 1:1 ratio by weight. Accordingly, the sample composition comprised 0.5% of the acrylamide polymer derivative (SCR-100™) bwoc and 0.5% of Universal Cement Systems™ multi-purpose cement additive bwoc. The thickening time was found to be 6 hours and 4 minutes at 220° F.

Sample Composition No. 3 was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, 0.85% of a set retarder composition of the present invention bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The set retarder composition of the present invention comprised an acrylamide polymer derivative (SCR-100™) and Universal Cement Systems™ multi-purpose cement additive in a 35:50 ratio by weight. Accordingly, the sample composition comprised 0.35% of the acrylamide polymer derivative (SCR-100™) bwoc and 0.50% of Universal Cement Systems™ multi-purpose cement additive bwoc. The thickening time was found to be 4 hours and 47 minutes at 220° F.

Sample Composition No. 4 was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, 0.73% of a set retarder composition of the present invention bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The components of the set retarder composition of the present invention were preblended and the set retarder composition was set aside for about 1 week prior to sample preparation. The set retarder composition of the present invention comprised 47.5% of an acrylamide polymer derivative (SCR-100™) by weight, 47.5% of Universal Cement Systems™ multi-purpose cement additive by weight, and 5% zeolite by weight. Accordingly, the sample composition comprised 0.35% of the acrylamide polymer derivative (SCR-100™) bwoc, 0.35% of Universal Cement Systems™ multi-purpose cement additive bwoc, and 0.03% zeolite bwoc. The thickening time was found to be 4 hours and 58 minutes at 220° F.

Sample Composition No. 5 was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, and 0.7% of a set retarder composition of the present invention bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The set retarder composition of the present invention comprised an acrylamide polymer derivative (SCR-100™) and Universal Cement Systems™ multi-purpose cement additive in a 1:1 ratio by weight. Accordingly, the sample composition comprised 0.35% of the acrylamide polymer derivative (SCR-100™) bwoc and 0.35% of Universal Cement Systems™ multi-purpose cement additive bwoc. The thickening time was found to be 5 hours and 1 minute at 220° F.

Sample Composition No. 6 was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, 0.73% of a set retarder composition of the present invention bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The components of the set retarder composition were preblended and the set retarder composition was set aside for about 1 week prior to sample preparation. The set retarder composition of the present invention comprised 47.5% of an acrylamide polymer derivative (SCR-100™) by weight, 47.5% of Universal Cement Systems™ multi-purpose cement additive by weight, and 5% of fine grain vitrified shale (PRESSURE-SEAL® FINE LCM) by weight. Accordingly, the sample composition comprised 0.35% of the acrylamide polymer derivative (SCR-100™) bwoc, 0.35% of Universal Cement Systems™ multi-purpose cement additive bwoc, and 0.03% fine grain vitrified shale bwoc. The thickening time was found to be 5 hours and 33 minutes at 220° F.

Sample Composition No. 7 (comparative) was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, 0.5% of a lignin-based retarder (HR-601) bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The thickening time was found to be 3 hours and 4 minutes at 220° F.

Sample Composition No. 8 was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, 0.73% of a set retarder composition of the present invention bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The components of the set retarder composition were preblended and the set retarder composition was set aside for about 1 week prior to sample preparation. The set retarder composition of the present invention comprised 47.5% of a lignin-based retarder (HR-601) by weight, and 47.5% of Universal Cement Systems™ multi-purpose cement additive by weight, and 5% zeolite by weight. Accordingly, the sample composition comprised 0.35% of a lignin-based retarder (HR-601) bwoc, 0.35% of Universal Cement Systems™ multi-purpose cement additive bwoc, and 0.03% zeolite bwoc. The thickening time was found to be 2 hours and 44 minutes at 220° F.

A summary of the composition of each of the samples is depicted below in Table 1.

TABLE 1 % Universal % SCR- % HR- Cement % Vitrified FLUID 100 ™ 601 Systems ™ % Zeolite Shale Sample 0.5 0 0 0 0 Composition No. 1 Sample 0.5 0 0.5 0 0 Composition No. 2 Sample 0.35 0 0.5 0 0 Composition No. 3 Sample 0.35 0 0.35 0.03 0 Composition No. 4 Sample 0.35 0 0.35 0 0 Composition No. 5 Sample 0.35 0 0.35 0 0.03 Composition No. 6 Sample 0 0.5 0 0 0 Composition No. 7 Sample 0 0.35 0.35 0.03 0 Composition No. 8

A summary of the thickening times and compressive strengths for each of the sample compositions is depicted below in Table 2.

TABLE 2 Time for Time for 500 psi 50 psi Compressive 12 Hour 24 Hour Thickening Compressive Strength Compressive Compressive Time at Strength at at Strength at Strength at 220° F. 250° F. 250° F. 250° F. 250° F. FLUID (hr:min) (hr:min) (hr:min) (psi) (psi) Sample 4:33 5:32 6:06 2000 3007 Composition No. 1 Sample 6:04 5:43 6:25 2200 3468 Composition No. 2 Sample 4:47 4:15 5:25 2220 3334 Composition No. 3 Sample 4:58 4:17 5:29 2300 3451 Composition No. 4 Sample 5:01 4:34 5:09 2287 3304 Composition No. 5 Sample 5:33 4:50 5:28 2217 3158 Composition No. 6 Sample 3:04 3:30 4:10 2435 3442 Composition No. 7 Sample 2:44 3:36 4:10 2544 3467 Composition No. 8

Therefore, Example 1 indicates, inter alia, that the use of a set retarder composition of the present invention comprised of a reduced dose of an acrylamide polymer derivative or lignin-based retarder delivers cement set retardation comparable to a larger dose of the acrylamide polymer derivative or lignin-based retarder.

EXAMPLE 2

Sample compositions were prepared according to the following procedure. Each sample was dry blended, then mixed for 35 seconds at 15,000 rpm in a Waring blender. The liquid components were mixed with the water prior to combination with the dry components. After sample preparation, compressive strength tests and thickening time tests were performed on each of the samples using an Ultrasonic cement analyzer according to API Specification 10A, Twenty-Third Edition, April, 2002. Furthermore, the time for each of the samples to reach a compressive strength of 50 psi and 500 psi, respectively, was recorded. Each sample composition was brought up to 220° F. and 3,000 psi in 60 minutes. Next, the sample compositions were brought up to 250° F. in 240 minutes while static. Thickening time tests were performed at 220° F.

Sample composition No. 9 (comparative) was prepared by mixing 0.12 gallons of an acrylamide polymer derivative (SCR-100™) per sack of cement with a 16.9 ppg slurry, the slurry comprised 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. Accordingly, as powdered equivalent, the sample composition comprised 0.5% of the acrylamide polymer derivative (SCR-100™) bwoc. The thickening time was found to be 5 hours and 6 minutes at 220° F.

Sample composition No. 10 was prepared by mixing 0.173 gallons of a set retarder composition of the present invention per sack of cement with 16.9 ppg slurry, the slurry comprised 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The set retarder composition of the present invention comprised an acrylamide polymer derivative (SCR-100™) and Universal Cement Systems™ multi-purpose cement additive in a 1:1 ratio by weight. Accordingly, as powdered equivalent, the sample composition comprised 0.35% of the acrylamide polymer derivative (SCR-100™) bwoc and 0.35% of Universal Cement Systems™ multi-purpose cement additive bwoc. The thickening time was found to be 5 hours and 15 minutes at 220° F.

Sample composition No. 11 was prepared by mixing 0.173 gallons of a set retarder composition of the present invention per sack of cement with 16.9 ppg slurry, the slurry comprising 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The set retarder composition was preblended and set a side for about one week prior to sample preparation. The set retarder composition of the present invention comprised an acrylamide polymer derivative (SCR-100™) and Universal Cement Systems™ multi-purpose cement additive in a 1:1 ratio by weight. Accordingly, as powdered equivalent, the sample composition comprised 0.35% of the acrylamide polymer derivative (SCR-100™) bwoc and 0.35% of Universal Cement Systems™ multi-purpose cement additive bwoc. The thickening time was found to be 5 hours and 20 minutes at 220° F.

A summary of the thickening times for each of the samples is depicted below in Table 3.

TABLE 3 Thickening % Universal Time at % SCR- Cement 220° F. FLUID 100 ™ Systems ™ (hr:min) Sample 0.5 0 5:06 Composition No. 9 Sample 0.35 0.35 5:15 Composition No. 10 Sample 0.35 0.35 5:20 Composition No. 11¹ The SCR-100 ™ and Universal Cement Systems ™ multi-purpose cement additive were preblended.

A summary of the compressive strengths for each of the samples is depicted below in Table 4.

TABLE 4 Time for Time for 500 50 psi psi 12 Hour 24 Hour % Compressive Compressive Compressive Compressive Universal Strength at Strength at Strength at Strength at % SCR- Cement 250° F. 250° F. 250° F. 250° F. FLUID 100 ™ Systems ™ (hr:min) (hr:min) (psi) (psi) Sample 0.5 0 5:20 6:02 2050 2978 Composition No. 9 Sample 0.35 0.35 4:31 5:07 2147 3222 Composition No. 10 Sample 0.35 0.35 4:17 5:07 2098 3055 Composition No. 11¹ ¹The SCR-100 ™ and Universal Cement Systems ™ multi-purpose cement additive were preblended.

Therefore, Example 2 indicates, inter alia, that the use of a set retarder composition of the present invention comprised of a reduced dose of an acrylamide polymer derivative delivers cement set retardation comparable to a larger dose of the acrylamide polymer derivative.

EXAMPLE 3

Sample compositions were prepared according to the following procedure. Each sample was dry blended, then mixed for 35 seconds at 15,000 rpm in a blender. Then, a static gel strength test was performed. The sample compositions were brought up to 220° F. and 10,400 psi in 60 minutes. The sample compositions were stirred for another 15 minutes and then brought up to 250° in 240 minutes while static.

Sample Composition No. 12 (comparative) was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, 0.5% of an acrylamide polymer derivative (SCR-100™) bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The zero-gel time was found to be 46 minutes and the transition time was found to be 30 minutes.

Sample Composition No. 13 was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 0.5% of HALAD® 344 fluid loss additive bwoc, 0.73% of a set retarder composition of the present invention bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The components of the set retarder composition were preblended and the set retarder composition was set aside for about 1 week prior to sample preparation. The set retarder composition of the present invention comprised 47.5% of an acrylamide polymer derivative (SCR-100™) by weight, and 47.5% of Universal Cement Systems™ multi-purpose cement additive by weight, and 5% zeolite by weight. Accordingly, the sample composition comprised 0.35% of the acrylamide polymer derivative (SCR-100™) bwoc, 0.35% of Universal Cement Systems™ multi-purpose cement additive bwoc, and 0.03% zeolite bwoc. The zero-gel time was found to be 68 minutes and the transition time was found to be 14 minutes.

A summary of the data from each of the samples is depicted in Table 5, below.

TABLE 5 % Universal Transition % SCR- Cement Zero-gel Time FLUID 100 ™ Systems ™ % Zeolite time (min) (min) Sample 0.5 0 0 46 30 Composition No. 12 Sample 0.35 0.35 0.03 68 14 Composition No. 13

Thus, Example 3 demonstrates, inter alia, that the use of a set retarder composition of the present invention comprised of a reduced dose of an acrylamide polymer derivative provides accelerated transition times and increased zero-gel times when compared to a larger dose of the acrylamide polymer derivative.

EXAMPLE 4

Sample compositions were prepared according to the following procedure. Each sample was dry blended, then mixed for 35 seconds at 15,000 rpm in a Waring blender. After sample preparation, compressive strength tests and thickening time tests were performed on each of the samples using an ultrasonic cement analyzer according to API Specification 10A, Twenty-Third Edition, April, 2002. Furthermore, the time for each of the samples to reach a compressive strength of 50 psi and 500 psi, respectively, was recorded. Each sample composition was brought up to 220° F. and 3,000 psi in 60 minutes. Next, the sample compositions were brought up to 250° F. in 240 minutes while static. Thickening time tests were performed at 220° F.

Sample Composition No. 14 (comparative) was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 1% of bentonite bwoc, 0.35% of an acrylamide polymer derivative (SCR-100™), Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The thickening time was found to be 4 hours and 30 minutes at 220° F.

Sample Composition No. 15 (comparative) was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 1% of bentonite bwoc, 0.50% of an acrylamide polymer derivative (SCR-100™), Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The thickening time was found to be 4 hours and 35 minutes at 220° F.

Sample Composition No. 16 was prepared by mixing 35% crystalline or non-crystalline silica bwoc, 1% of bentonite bwoc, 0.73% of a set retarder composition of the present invention bwoc, Texas Lehigh Class H cement, and sufficient water to provide a 16.9 ppg slurry. The components of the set retarder composition were preblended and the set retarder composition was set aside for about 1 week prior to sample preparation. The set retarder composition of the present invention comprised 47.5% of an acrylamide polymer derivative (SCR-100™) by weight, 47.5% of Universal Cement Systems™ multi-purpose cement additive by weight, and 5% zeolite by weight. Accordingly, the sample composition comprised 0.35% of the acrylamide polymer derivative (SCR-100™) bwoc, 0.35% of Universal Cement Systems™ multi-purpose cement additive bwoc, and 0.03% zeolite bwoc. The thickening time was found to be 5 hours and 33 minutes at 220° F.

A summary of the thickening times for each of the samples is depicted below in Table 6.

TABLE 6 Thickening % Universal Time at % SCR- Cement 220° F. FLUID 100 ™ Systems ™ (hr:min) Sample 0.35 0 4:30 Composition No. 14 Sample 0.5 0 4:35 Composition No. 15 Sample 0.35 0.35 5:33 Composition No. 16

A summary of the compressive strengths for each of the samples is depicted below in Table 7.

TABLE 7 Time for Time for 500 50 psi psi 12 Hour 24 Hour % Compressive Compressive Compressive Compressive Universal Strength at Strength at Strength at Strength at % SCR- Cement 250° F. 250° F. 250° F. 250° F. FLUID 100 ™ Systems ™ (hr:min) (hr:min) (psi) (psi) Sample 0.35 0 4:50 5:20 2447 3485 Composition No. 14 Sample 0.5 0 5:03 5:41 2500 3625 Composition No. 15 Sample 0.35 0.35 5:00 5:35 2545 3509 Composition No. 15

Therefore, Example 4 indicates, inter alia, that the use of a set retarder composition of the present invention comprised of a reduced dose of an acrylamide polymer derivative delivers cement set retardation comparable to a larger dose of the acrylamide polymer derivative.

Therefore, the present invention is well adapted to carry out the objects and attain the ends and advantages mentioned as well as those that are inherent therein. While numerous changes may be made by those skilled in the art, such changes are encompassed within the spirit of this invention as defined by the appended claims. 

1. A method of cementing in a subterranean formation comprising: providing a cement composition comprising a cement comprising an API cement, water, and a set retarder composition, the set retarder composition comprising: an acrylamide polymer derivative, and an iron compound present in the range of at least about 0.24% by weight of the set retarder composition; placing the cement composition into the subterranean formation; and permitting the cement composition to set therein.
 2. The method of claim 1 wherein the API cement comprises a Class A Portland cement, a Class B Portland cement, a Class C Portland cement, a Class G Portland cement, a Class H Portland cement, a Class J Portland cement, or an equivalent thereof.
 3. The method of claim 1 wherein the set retarder composition further functions as a dispersant, as a free flow additive, to accelerate the transition time of the cement composition, or a combination thereof.
 4. The method of claim 1 wherein the acrylamide polymer derivative comprises monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof.
 5. The method of claim 1 wherein the acrylamide polymer derivative comprises a copolymer comprising first monomers formed from a hydrolyzed acrylamide, a partially hydrolyzed acrylamide, a hydrolyzed acrylamide derivative, or a partially hydrolyzed acrylamide derivative and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof.
 6. The method of claim 1 wherein the acrylamide polymer derivative comprises a copolymer comprising first monomers formed from acrylic acid and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof.
 7. The method of claim 6 wherein the second monomers are present in the copolymer in an amount in the range of from about 40 mole percent to about 60 mole percent.
 8. The method of claim 6 wherein the second monomers are present in the copolymer in an amount in the range of from about 45 mole percent to about 55 mole percent.
 9. The method of claim 1 wherein the acrylamide polymer derivative comprises a copolymer comprising first monomers formed from a first acid and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof, wherein the first acid is represented by the formula:

wherein R₁ is H or CH₃, R₂ is H or COOH, R₃ is H or COOH, and R₄ is H, COOH, or CH₂COOH; provided that when R₁ is H and R₂ is COOH, R₃ and R₄ are different and are either H or COOH; when R₁ and R₂ are both H, R₃ is COOH and R₄ is CH₂COOH; and when R₁ is CH₃, R₂ is COOH and R₃ and R₄ are different and are either H or COOH.
 10. The method of claim 9 wherein the first acid is maleic acid, itaconic acid, fumaric acid, citraconic acid, or mesaconic acid.
 11. The method of claim 9 wherein the first monomers are present in the copolymer in an amount in the range of from about 5 mole percent to about 50 mole percent.
 12. The method of claim 9 wherein the first monomers are present in the copolymer in an amount in the range of from about 30 mole percent to about 50 mole percent.
 13. The method of claim 1 wherein the acrylamide polymer derivative comprises a terpolymer comprising first monomers formed from a first acid, second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof, and third monomers different from the first monomers and the second monomers, wherein the first acid is represented by the formula:

wherein R₁ is H or CH₃, R₂ is H or COOH, R₃ is H or COOH, and R₄ is H, COOH, or CH₂COOH; provided that when R₁ is H and R₂ is COOH, R₃ and R₄ are different and are either H or COOH; when R₁ and R₂ are both H, R₃ is COOH and R₄ is CH₂COOH; and when R₁ is CH₃, R₂ is COOH and R₃ and R₄ are different and are either H or COOH.
 14. The method of claim 13 wherein the third monomers comprise at least one of the following: maleic acid, acrylic acid, sodium methallyl sulfonate, sodium-p-sulfophenyl methallyl ether, sodium p-vinyl benzene sulfonate, acrylamide, N,N-dimethylacrylamide, vinyl sulfonic acid, acrylonitrile, 1-vinyl-2-pyrrolidone, vinyl phosphonic acid, diallydimethylammonium chloride, water soluble acrylates, a methacrylates, an acrylamide derivative, dimethylaminoethyl methacrylatemethylchloride, diethylaminoethyl methacrylate, dimethyl aminoethyl acrylate methyl chloride, N-dimethyl aminopropyl methacrylamide, methacrylamido propyltrimethyl ammonium chloride, N,N-dimethylaminoethyl methacrylate, or 2-triethylammoniummethyl methacrylate chloride.
 15. The method of claim 13 wherein the first acid is maleic acid, itaconic acid, fumaric acid, citraconic acid, or mesaconic acid.
 16. The method of claim 13 wherein the first monomers are present in the terpolymer in an amount in the range of from about 5 mole percent to about 50 mole percent, the second monomers are present in the terpolymer in an amount in the range of from about 90 mole percent to about 45 mole percent, and the third monomers may be present in the terpolymer in an amount in the range of from about 5 mole percent to about 50 mole percent.
 17. The method of claim 1 wherein the acrylamide polymer derivative has a weight average molecular weight of less than about 50,000.
 18. The method of claim 1 wherein the acrylamide polymer derivative is present in the set retarder composition in an amount in the range of from about 1 percent to about 95 percent by weight.
 19. The method of claim 1 wherein the acrylamide polymer derivative is present in the set retarder composition in an amount in the range of from about 30 percent to about 60 percent by weight.
 20. The method of claim 1 wherein the iron compound is present in the set retarder composition in an amount in the range of from about 5 percent to about 25 percent by weight.
 21. The method of claim 1 wherein the iron compound is present in the set retarder composition in an amount in the range of from about 10 percent to about 15 percent by weight.
 22. The method of claim 1 wherein the iron compound comprises a soluble iron compound.
 23. The method of claim 1 wherein the iron compound comprises an iron chloride or an iron gluconate.
 24. The method of claim 23 wherein the iron chloride comprises ferric chloride, ferrous chloride, or a mixture thereof.
 25. The method of claim 1 wherein the set retarder composition further comprises a hydratable polymer.
 26. The method of claim 25 wherein the hydratable polymer comprises carboxymethylcellulose, hydroxyethylcellulose, carboxymethylhydroxyethylcellulose, a vinyl sulfonated polymer, a hydratable graft polymer, or a mixture thereof.
 27. The method of claim 25 wherein the hydratable polymer is present in the set retarder composition in an amount in the range of from about 0.1 percent to about 15 percent by weight.
 28. The method of claim 1 wherein the set retarder composition further comprises a dispersant.
 29. The method of claim 28 wherein the dispersant is present in the set retarder composition in an amount in the range of from about 5 percent to about 70 percent by weight.
 30. The method of claim 28 wherein the dispersant comprises a water-soluble polymer prepared by the caustic-catalyzed condensation of formaldehyde with acetone wherein the polymer contains sodium sulfate groups.
 31. The method of claim 1 wherein the set retarder composition further comprises a zeolite.
 32. The method of claim 31 wherein the zeolite comprises chabazite and amorphous silica.
 33. The method of claim 31 wherein the zeolite is present in the set retarder composition in an amount in the range of from about 0.1 percent to about 15 percent by weight.
 34. The method of claim 1 wherein the set retarder composition further comprises a shale.
 35. The method of claim 34 wherein the shale is a vitrified shale.
 36. The method of claim 34 wherein the shale is present in the set retarder composition in an amount in the range of from about 0.1 percent to about 15 percent by weight.
 37. The method of claim 1 wherein the set retarder composition further comprises an organic acid.
 38. The method of claim 37 wherein the organic acid is present in the set retarder composition in an amount in the range of from about 0.01 percent to about 5 percent by weight.
 39. The method of claim 1 wherein the set retarder composition further comprises a silica, a deaggregation agent, or a mixture thereof.
 40. The method of claim 39 wherein the silica is a high surface area amorphous silica.
 41. The method of claim 40 wherein the high surface area amorphous silica is present in the set retarder composition in an amount in the range of from about 0.1 percent to about 15 percent by weight.
 42. The method of claim 39 wherein the deaggregation agent is present in the set retarder composition in an amount in the range of from about 1 percent to about 15 percent by weight.
 43. The method of claim 1 wherein the set retarder composition is present in the cement composition in an amount in the range of from about 0.01 percent by weight of the cement to about 5 percent by weight of the cement.
 44. The method of claim 1 wherein the set retarder composition further comprises a hydratable polymer, an organic acid, a dispersant, or a mixture thereof.
 45. The method of claim 44 wherein the set retarder composition further comprises a zeolite, a shale, a deaggregation agent, a silica, or a mixture thereof.
 46. The method of claim 1 wherein the set retarder composition is present in the cement composition in an amount in the range of from about 0.1 percent to about 5 percent by weight of the cement; wherein the acrylamide polymer derivative is present in the set retarder composition in an amount in the range of from about 40 percent to about 50 percent by weight; wherein the iron compound is present in the set retarder composition in an amount in the range of from about 10 percent by weight to about 15 percent by weight; wherein the set retarder composition further comprises a dispersant, wherein the dispersant is present in the set retarder composition in an amount in the range of from about 20 percent to about 40 percent by weight; and wherein the set retarder composition further comprises a hydratable polymer, wherein the hydratable polymer is present in the set retarder composition in an amount in the range of from about 1.0 percent to about 5 percent by weight.
 47. A method of cementing in a subterranean formation comprising: providing a cement composition comprising a cement comprising a cement, water, and a set retarder composition, the set retarder composition comprising: a lignin-based retarder, and an iron compound; placing the cement composition into the subterranean formation; and permitting the cement composition to set therein.
 48. The method of claim 47 wherein the lignin-based retarder comprises a lignosulfonate and a sulfonated lignin.
 49. The method of claim 48 wherein the sulfonated lignin contains at least about 2% organic sulphur.
 50. The method of claim 48 wherein the lignin-based retarder further comprises a sugar acid.
 51. The method of claim 50 wherein the sugar acid is xylose sugar acid.
 52. The method of claim 47 wherein the lignin-based retarder is present in the set retarder composition in an amount in the range of from about 1 percent to about 95 percent by weight.
 53. The method of claim 47 wherein the lignin-based retarder is present in the set retarder composition in an amount in the range of from about 30 percent to about 60 percent by weight.
 54. The method of claim 47 wherein the iron compound is present in the set retarder composition in an amount in the range of from about 5 percent to about 25 percent by weight.
 55. The method of claim 47 wherein the iron compound comprises a soluble iron compound.
 56. The method of claim 47 wherein the iron compound comprises an iron chloride or an iron gluconate.
 57. The method of claim 47 wherein the set retarder composition further comprises a hydratable polymer, a dispersant, an organic acid, a silica, a deaggregation agent, or a combination thereof.
 58. The method of claim 57 wherein the hydratable polymer comprises carboxymethylcellulose, hydroxyethylcellulose, carboxymethylhydroxyethylcellulose, a vinyl sulfonated polymer, a hydratable graft polymer, or a mixture thereof.
 59. The method of claim 57 wherein the hydratable polymer is present in the set retarder composition in an amount in the range of from about 0.1 percent to about 15 percent by weight.
 60. The method of claim 57 wherein the dispersant is present in the set retarder composition in an amount in the range of from about 5 percent to about 70 percent by weight.
 61. The method of claim 57 wherein the dispersant comprises a water-soluble polymer prepared by the caustic-catalyzed condensation of formaldehyde with acetone wherein the polymer contains sodium sulfate groups.
 62. The method of claim 57 wherein the organic acid is present in the set retarder composition in an amount in the range of from about 0.01 percent to about 5 percent by weight.
 63. The method of claim 57 wherein the silica is a high surface area amorphous silica.
 64. The method of claim 57 wherein the high surface area amorphous silica is present in the set retarder composition in an amount in the range of from about 0.1 percent to about 15 percent by weight.
 65. The method of claim 57 wherein the deaggregation agent is present in the set retarder composition in an amount in the range of from about 1 percent to about 15 percent by weight.
 66. The method of claim 47 wherein the set retarder composition further comprises at a zeolite, a shale, or a combination thereof.
 67. The method of claim 66 wherein the zeolite is present in the set retarder composition in an amount in the range of from about 0.1 percent to about 15 percent by weight.
 68. The method of claim 66 wherein the shale is a vitrified shale.
 69. The method of claim 66 wherein the shale is present in the set retarder composition in an amount in the range of from about 0.1 percent to about 15 percent by weight.
 70. The method of claim 47 wherein the set retarder composition is present in the cement composition in an amount in the range of from about 0.01 percent by weight of the cement to about 5 percent by weight of the cement.
 71. A method of retarding the set time of a cement composition comprising: adding a set retarder composition to a cement composition, the set retarder composition comprising an acrylamide polymer derivative, and an iron compound; present in the range of at lest about 0.24% by weight of the set retarder composition; placing the cement composition into the subterranean formation; and permitting the cement composition to set therein.
 72. The method of claim 71 wherein the acrylamide polymer derivative comprises monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof.
 73. The method of claim 71 wherein the acrylamide polymer derivative comprises a copolymer comprising first monomers formed a hydrolyzed acrylamide, a partially hydrolyzed acrylamide, a hydrolyzed acrylamide derivative, or a partially hydrolyzed acrylamide derivative and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof.
 74. The method of claim 71 wherein the acrylamide polymer derivative comprises a copolymer comprising first monomers formed from acrylic acid and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof.
 75. The method of claim 71 wherein the acrylamide polymer derivative comprises a copolymer comprising first monomers formed from a first acid and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof, wherein the first acid is represented by the formula:

wherein R₁ is H or CH₃, R₂ is H or COOH, R₃ is H or COOH, and R₄ is H, COOH, or CH₂COOH; provided that when R₁ is H and R₂ is COOH, R₃ and R₄ are different and are either H or COOH; when R₁ and R₂ are both H, R₃ is COOH and R₄ is CH₂COOH; and when R₁ is CH₃, R₂ is COOH and R₃ and R₄ are different and are either H or COOH.
 76. The method of claim 71 wherein the acrylamide polymer derivative comprises a terpolymer comprising first monomers formed from a first acid, second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof, and third monomers different from the first monomers and the second monomers, wherein the first acid is represented by the formula:

wherein R₁ is H or CH₃, R₂ is H or COOH, R₃ is H or COOH, and R₄ is H, COOH, or CH₂COOH; provided that when R₁ is H and R₂ is COOH, R₃ and R₄ are different and are either H or COOH; when R₁ and R₂ are both H, R₃ is COOH and R₄ is CH₂COOH; and when R₁ is CH₃, R₂ is COOH and R₃ and R₄ are different and are either H or COOH.
 77. The method of claim 71 wherein the set retarder composition further comprises a hydratable polymer, an organic acid, a dispersant, a zeolite, a shale, a deaggregation agent, a silica, or a combination thereof.
 78. A method of preparing a cement composition comprising: preblending a set retarder composition that comprises an acrylamide polymer derivative and an iron compound present in the range of at lest about 0.24% by weight of the set retarder composition; and preparing a cement composition that comprises the set retarder composition, a cement, and water, subsequent to preblending the set retarder composition.
 79. The method of claim 78 wherein the acrylamide polymer derivative comprises monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof.
 80. The method of claim 78 wherein the acrylamide polymer derivative comprises a copolymer comprising first monomers formed from a hydrolyzed acrylamide, a partially hydrolyzed acrylamide, a hydrolyzed acrylamide derivative, or a partially hydrolyzed acrylamide derivative and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof.
 81. The method of claim 78 wherein the acrylamide polymer derivative comprises a copolymer comprising first monomers formed from acrylic acid and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof.
 82. The method of claim 78 wherein the acrylamide polymer derivative comprises a copolymer comprising first monomers formed from a first acid and second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof, wherein the first acid is represented by the formula:

wherein R₁ is H or CH₃, R₂ is H or COOH, R₃ is H or COOH, and R₄ is H, COOH, or CH₂COOH; provided that when R₁ is H and R₂ is COOH, R₃ and R₄ are different and are either H or COOH; when R₁ and R₂ are both H, R₃ is COOH and R₄ is CH₂COOH; and when R₁ is CH₃, R₂ is COOH and R₃ and R₄ are different and are either H or COOH.
 83. The method of claim 78 wherein the acrylamide polymer derivative comprises a terpolymer comprising first monomers formed from a first acid, second monomers formed from 2-acrylamido-2-methylpropane sulfonic acid or a derivative thereof, and third monomers different from the first monomers and the second monomers, wherein the first acid is represented by the formula:

wherein R₁ is H or CH₃, R₂ is H or COOH, R₃ is H or COOH, and R₄ is H, COOH, or CH₂COOH; provided that when R₁ is H and R₂ is COOH, R₃ and R₄ are different and are either H or COOH; when R₁ and R₂ are both H, R₃ is COOH and R₄ is CH₂COOH; and when R₁ is CH₃, R₂ is COOH and R₃ and R₄ are different and are either H or COOH.
 84. The method of claim 83 wherein the third monomers are formed from maleic acid, acrylic acid, sodium methallyl sulfonate, sodium-p-sulfophenyl methallyl ether, sodium p-vinyl benzene sulfonate, acrylamide, N,N-dimethylacrylamide, vinyl sulfonic acid, acrylonitrile, 1-vinyl-2-pyrrolidone, vinyl phosphonic acid, diallydimethylammonium chloride, a water-soluble acrylate, a methacrylate, an acrylamide derivative, dimethylaminoethyl methacrylatemethylchloride, diethylaminoethyl methacrylate, dimethyl aminoethyl acrylate methyl chloride, N-dimethyl aminopropyl methacrylamide, methacrylamido propyltrimethyl ammonium chloride, N,N-dimethylaminoethyl methacrylate, or 2-triethylammoniummethyl methacrylate chloride.
 85. The method of claim 78 wherein the acrylamide copolymer derivative has a weight average molecular weight of less than about 50,000.
 86. The method of claim 78 wherein the acrylamide polymer derivative is present in the set retarder composition in an amount in the range of from about 30 percent to about 60 percent by weight.
 87. The method of claim 78 wherein the iron compound is present in the set retarder composition in an amount in the range of from about 5 percent to about 25 percent by weight.
 88. The method of claim 78 wherein the iron compound comprises a soluble iron compound.
 89. The method of claim 78 wherein the iron compound comprises an iron chloride or an iron gluconate.
 90. The method of claim 78 wherein the iron chloride comprises ferric chloride, ferrous chloride, or a mixture thereof.
 91. The method of claim 78 wherein the set retarder composition further comprises a hydratable polymer.
 92. The method of claim 91 wherein the hydratable polymer comprises carboxymethylcellulose, hydroxyethylcellulose, carboxymethylhydroxyethylcellulose, a vinyl sulfonated polymer, a hydratable graft polymer, or a mixture thereof.
 93. The method of claim 78 wherein the set retarder composition further comprises a dispersant.
 94. The method of claim 93 wherein the dispersant comprises a water-soluble polymer prepared by the caustic-catalyzed condensation of formaldehyde with acetone wherein the polymer contains sodium sulfate groups.
 95. The method of claim 78 wherein the set retarder composition further comprises a zeolite.
 96. The method of claim 95 wherein the zeolite comprises chabazite and amorphous silica.
 97. The method of claim 78 wherein the set retarder composition further comprises a shale.
 98. The method of claim 97 wherein the shale is a vitrified shale.
 99. The method of claim 78 wherein the set retarder composition further comprises an organic acid.
 100. The method of claim 78 wherein the set retarder composition further comprises a silica, a deaggregation agent, or a combination thereof.
 101. The method of claim 78 wherein the set retarder composition is present in the cement composition in an amount in the range of from about 0.01 percent by weight of the cement to about 5 percent by weight of the cement.
 102. The method of claim 78 wherein the set retarder composition further comprises an organic acid, a dispersant, or a combination thereof.
 103. The method of claim 102 further wherein the set retarder composition further comprises a zeolite, a shale, a deaggregation agent, a silica, or a combination thereof. 